The present invention relates to a silicone compound having high affinity for various unctuous agents, such as silicone oils, and excellent emulsifying capability, and further to cosmetic materials containing such a silicone compound.
In recent years, silicone oils have been used as an unctuous agent mixed in emulsified compositions of water-in-oil type to ensure no greasiness, less tackiness and good water repellency for the emulsified compositions. However, it is still difficult to impart good stability to water-in-oil emulsions containing silicone oils by the use of conventional emulsifiers, such as polyoxyalkylene fatty acid esters.
So the methods of using polyoxyalkylene-modified organopolysiloxanes (polyether-modified silicones) highly compatible with silicone oils as surfactants in water-in-oil emulsions have been proposed in, e.g., JP-A-61-293903, JP-A-61-293904, JP-A-62-187406, JP-A-62-215510 and JP-A-62-216635 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published Japanese patent application). However, not only silicone oils alone but also mixtures with ester oils and hydrocarbon oils are used in many of emulsions for cosmetics use. In water-in-oil emulsions using those oil mixtures as an unctuous agent, the foregoing polyether-modified silicone surfactants have inferior power of emulsification, so they are difficult to impart satisfactory stability to the emulsions of the aforementioned type.
As a method for solving the foregoing problem, the method of using as an emulsifier an organopolysiloxane having both long-chain alkyl and polyoxyalkylene groups, which is represented by the following formula, is proposed in JP-A-61-90732. 
Although the organopolysiloxane compounds represented by the foregoing formula have excellent emulsifying power in systems containing mixed oils rich in ester oil and hydrocarbon oil, they have a drawback of sometimes failing to ensure high stability and no change upon storage for the systems containing mixed oils rich in silicone oils. Therefore, it has been desired to develop emulsifiers suitable for cosmetic materials, namely compounds having excellent capability to emulsify conventional unctuous agents, such as silicone oils, ester oils and hydrocarbon oils, for general cosmetics use to ensure high storage stability of the cosmetic materials.
A first object of the present invention is to provide a silicone compound having a great capability to emulsify various unctuous agents, including silicone oils, for cosmetics use and ensuring high emulsion stability.
A second object of the invention is to provide a cosmetic material which has high stability in an emulsified state to ensure satisfactory storage stability.
As a result of our intensive studies to attain the aforementioned objects, it has been found that the silicone compounds produced by addition of polyoxyalkylene compounds and silicone compounds to organohydrogenpolysiloxanes have a very strong affinity for silicone oils to ensure a great capability to emulsify them, and so when they are used as emulsifier the resultant emulsions can have very good stability. Further, it has also been found that the silicone compounds produced by addition of long-chain alkyl group-containing organic compounds besides polyoxyalkylene compounds and silicone compounds to organohydrogenpolysiloxanes have a very strong affinity for unctuous agents used in general cosmetic materials, including silicone oils, ester oils and hydrocarbon oils, to ensure a great capability to emulsify them, and so when they are used as emulsifier the resultant emulsions can have very good stability and a high degree of effectiveness for cosmetics use, thereby achieving the present invention.
While such silicone compounds as to be produced by the addition reaction of silicone compounds to organohydrogenpolysiloxanes are disclosed in JP-A-7-197055 as actuation silicone oils having good low temperature characteristics, it is our finding that those silicone compounds are particularly effective as ingredients of cosmetic materials. Further, we have found that, when the aforementioned silicone compounds have relatively low molecular weight, they are instrumental in cleansing not only sebum stains but also makeup stains from cosmetics of the type which are hard to come off, and besides, the cleansing composition comprising them has a very good touch during and after cleansing treatment.
The present invention thus provides a silicone compound represented by the following formula (1), and cosmetic materials containing such a silicone compound:
R1aR2bR3cSiO(4xe2x88x92axe2x88x92bxe2x88x92c)/2xe2x80x83xe2x80x83(1)
wherein
R1 groups, which are the same or different, are each an organic group selected from the class consisting of 1-30C alkyl groups, aryl groups, aralkyl groups, fluorinated alkyl groups and organic groups represented by the following formula (2),
xe2x80x94CmH2mxe2x80x94Oxe2x80x94(C2H4O)d(C3H6O)eR4xe2x80x83xe2x80x83(2);
R2 groups are polyoxyalkylene moiety-containing organic groups represented by the following formula (3),
xe2x80x94CmH2mxe2x80x94Oxe2x80x94(C2H4O)f(C3H6O)gR5xe2x80x83xe2x80x83(3);
R3 groups are organosiloxane compound residues represented by the following formula (4), 
R4 represents a 4-30C hydrocarbon group or an acyl group represented by R6xe2x80x94COxe2x80x94; R5 represents a hydrogen atom, a 1-30C hydrocarbon group or an acyl group represented by R6xe2x80x94COxe2x80x94; R6 represents a 1-30C hydrocarbon group; a, b and c are values in the ranges 1.0xe2x89xa6axe2x89xa62.5, 0.001xe2x89xa6bxe2x89xa61.5 and 0.001xe2x89xa6cxe2x89xa61.5; d and e are each an integer of from 0 to 50; f is an integer of from 2 to 200 and g is an integer of from 0 to 200, provided that the sum of f and g is an integer of from 3 to 200; m is an integer of from 0 to 15; h is an integer of from 0 to 500; and n is an integer of from 1 to 5.
R1 groups in formula (1) may be the same or different, and each of them represents a 1-30C alkyl group, an aryl group, an aralkyl group, a fluorinated alkyl group or an organic group represented by formula (2). Examples of an alkyl group represented by R1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl octyl, nonyl, decyl, cyclopentyl and cyclohexyl groups; those of an aryl group include phenyl and tolyl groups; those of an aralkyl group include benzyl and phenetyl groups; and those of a fluorinated alkyl group include trifluoropropyl and heptadecafluorodecyl groups.
The organic group xe2x80x94CmH2mxe2x80x94Oxe2x80x94(C2H4O)d(C3H6O)eR4 (formula (2)), represented by R1 includes an alkoxy group, an acyloxy group, an alkenyl ether residue and an alkenyl ester residue. Additionally, R4 in formula (2) represents a monovalent 4-30C hydrocarbon group or an acyl group of formula R6COxe2x80x94 (wherein R6 is a 1-30C hydrocarbon group), d and e in formula (2) are each an integer of from 0 to 50, and m in formula (2) is an integer of from 0 to 15.
More specifically, when m, d and e are all zero, the formula (2) represents a 4-30 C alkoxy group including from lower alkoxy groups, such as butoxy and pentoxy, to higher alkoxy groups such as oleyloxy and stearoxy, or an acyloxy group such as a residue of acetic, lactic, butyric, oleic, stearic or behenic acid.
When m is not zero but d and e are zero, m is preferably 3, 5 or 11. In such a case, R1 represents a 1- or 2-propenyl ether residue, a pentenyl ether residue, or an undecenyl ether residue. When R4 is a hydrdocarbon group, such an ether residue is, e.g., an allyl stearyl ether residue, a pentenyl behenyl ether residue or an undecenyl oleyl ether residue. When d or e is not zero, the formula (2) assumes such a form that polyoxyalkylene is cut in an ether or ester linkage.
When m is 0, irrespective of the values of d and e, R1 of formula (2) tends to have inferior resistance to hydrolysis; while, when m is greater than 15, the resultant silicone compound has a strong oily smell. It is therefore advantageous for m to be from 3 to 11.
For the present silicone compound, it is desirable that at least 50% of R1 groups, preferably at least 70% of R1 groups, be methyl groups. Also, 100% of R1 groups in the present silicone compound may be methyl groups.
R2 groups are polyoxyalkylene moiety-containing organic groups of formula xe2x80x94CmH2mxe2x80x94Oxe2x80x94(C2H4O)f(C3H6O)gR5 (formula (3)). R5 in formula (3) is a hydrogen atom, a 1-30C hydrocarbon group or an acyl group represented by R6COxe2x80x94 wherein R6 is a 1-30C hydrocarbon group. The letter f in formula (3) is an integer from 2 to 200, preferably from 5 to 100, and the letter g in formula (3) is an integer of from 0 to 200, preferably from 0 to 100, provided that the sum of f and g is in the range of 3 to 200, preferably 5 to 100. When f/gxe2x89xa71, R2 groups can impart high affinity for water enough to form a water-in-oil emulsion to the present silicone compound. When both ethylene oxide units and propylene oxide units constitute the polyoxyalkylene moiety in formula (3), those units may take the form of either block or random copolymer.
R3 groups in formula (1) are organosiloxane compound residues represented by the following formula (4): 
wherein R1 has the same meaning as in formula (1), and h is an integer of from 0 to 500, preferably from 3 to 100, and n is an integer of from 1 to 5. For instance, n is 2 when the R3 group is a residue of the organosiloxane compound prepared by reaction of vinyl group with a hydrogensiloxane compound. In the case where h is greater than 500, the organosiloxane compounds tend to have a problem that their reactivity to organohydrogenpolysiloxane to constitute the main chain of the present silicone compound become low.
In formula (1), the letter a represents a value of from 1.0 to 2.5, preferably from 1.2 to 2.3. When the letter a is smaller than 1.0, the silicone compound is inferior in compatibility with an unctuous agent, and so it is difficult to ensure satisfactory stability in water-in-oil emulsions. When the letter a is greater than 2.5, on the other hand, the silicone compound has poor affinity for water, so it is also difficult to ensure satisfactory stability in water-in-oil emulsions. The letter b in formula (1) represents a value of from 0.001 to 1.5, preferably from 0.05 to 1.0. When b is smaller than 0.001, the silicone compound has poor affinity for water, and so it is difficult to ensure satisfactory stability in water-in-oil emulsions; while, when b is greater than 1.5, the silicone compound has too high affinity for water to impart satisfactory stability to water-in-oil emulsions. The letter c in formula (1) represents a value of from 0.001 to 1.5, preferably from 0.05 to 1.0. When c is smaller than 0.001, the silicone compound is inferior in compatibility with silicone oils, and so it is difficult to ensure satisfactory stability in water-in-oil emulsions. When c is greater than 1.5, on the other hand, the silicone compound has poor affinity for water, so it is also difficult to ensure satisfactory stability in water-in-oil emulsions.
When the present silicone compound is employed as an emulsifier, it has no particular restriction as to weight average molecular weight, but its weight average molecular weight is preferably in the range of 500 to 200,000, particularly 1,000 to 100,000.
In the cases where the present silicone compound is mixed in skin cleansing compositions, on the other hand, its appropriate weight average molecular weight is at most 4,000, preferably at most 2,000, particularly preferably at most 1,500.
The present silicone compound represented by formula (1) can be easily synthesized by subjecting organohydrogenpolysiloxanes to addition reaction with a polyoxyalkylene compound represented by the following formula (5) and an organosiloxane compound represented by the following formula (6), and further, if desired, an alkylene compound and/or an organic compound represented by the following formula (7) in the presence of a platinum or rhodium catalyst:
CmH(2mxe2x88x921)xe2x80x94Oxe2x80x94(C2H4O)f(C3H6O)gxe2x80x94R5xe2x80x83xe2x80x83(5)
xe2x80x83CmH(2mxe2x88x921)xe2x80x94Oxe2x80x94(C2H4O)d(C3H6O)exe2x80x94R4xe2x80x83xe2x80x83(7)
wherein R1, R4, R5, d, e, f, g, h, m and n have the same meanings as defined above respectively.
The organohydrogenpolysiloxanes used in the foregoing addition reaction may be either straight-chain or cyclic ones. From the viewpoint of smooth progress of the addition reaction, straight-chain organohydrogenpolysiloxanes are used to advantage.
In the addition reaction, it is appropriate to use the foregoing compounds in such amounts that the ratio of the total amount of compounds to be added, namely polyoxyalkylene compounds of formula (5), organosiloxane compounds of formula (6), and alkylene compounds and/or organic compounds of formula (7), to the amount of organohydrogenpolysiloxanes is from 0.5 to 2.0, preferably from 0.8 to 1.2, expressed in terms of the total mole number of terminal unsaturated bonds present in the compounds per mole of SiH groups.
The addition reaction is effectively performed in the presence of a platinum catalyst or a rhodium catalyst. Suitable examples of such a catalyst include chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinylsiloxane complex. The amount of catalyst used, though may be a catalytic amount, is specifically at most 50 ppm, preferably at most 20 ppm, based on the platinum or rhodium.
The aforementioned addition reaction may be carried out in an organic solvent, if desired. Examples of an organic solvent usable therein include aliphatic alcohols, such as methanol, ethanol, 2-propanol and butanol; aromatic hydrocarbons, such as toluene and xylene; aliphatic or alicyclic hydrocarbons, such as n-pentane, n-hexane and cyclohexane; and halogenated hydrocarbons, such as dichloromethane, chloroform and carbon tetrachloride. In the case of applying the present silicone compound to cosmetics, ethanol and 2-propanol (isopropyl alcohol) are used to advantage. The addition reaction has no particular limitations on reaction conditions, but it is preferably carried out for 1 to 10 hours under reflux.
The present silicone compounds can be used for various purposes. In particular, they are suitable as materials for all of cosmetics applied to skin and hair. In mixing the silicone compound of formula (1) in a cosmetic material, the proportion thereof is preferably from 0.1 to 40% by weight to the total ingredients in the cosmetic material.
To the present cosmetic materials, the ingredients used in general cosmetic materials, such as water, powders, alcohols, water-soluble polymers, film-forming agents, unctuous agents, oil-soluble gelling agents, clay minerals modified with organic compounds, surfactants, resins, ultraviolet absorbents, moisture-holding agents, antiseptics, antimicrobial agents, perfume, salts, antioxidants, pH regulators, chelating agents, refrigerants, anti-inflammatory agents, skin beautifying components (a skin whitener, a cell activator, a rough dry skin improver, a blood circulation promoter, a skin astringent and an anti-seborrheic agent), vitamins, amino acids, nucleic acids, hormones and clathrate compounds, can be added so far as they have no adverse influence on the effects of the present invention.
The powders used in the present cosmetic materials may be any powders so far as they are known to be used in conventional cosmetic materials, irrespective of their shape (whether it is spherical, acicular or tabular), their size (whether it is on the order of fume, fine grain or pigment), and their structure (whether it is porous or nonporous). Specifically, the powders usable in the invention include inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metallic powder pigments and natural colors.
Examples of inorganic powders usable in the present cosmetic materials include titanium dioxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, ruby mica, biotite, lipidolite, silicic acid, silicic acid anhydride, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal salts of tungstic acid, hydroxyapatite, vermiculite, haidilite, bentonite, montmorillonite, hectorite, zeolite, ceramics powder, calcium secondary phosphate, alumina, aluminum hydroxide, boron nitride and silica.
Examples of organic powders usable in the present cosmetic materials include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate powder, cellulose powder, silk powder, nylon powder such as 12-nylon powder or 6-nylon powder, styrene-acrylic acid copolymer powder, divinylbenzene-styrene copolymer powder, vinyl resin powder, urea resin powder, phenol resin powder, fluororesin powder, silicone resin powder, acrylic resin powder, melamine resin powder, epoxy resin powder, polycarbonate resin powder, microcrystalline fiber powder, starch powder and lauroyl lysine powder.
Examples of surfactant metal salt powders (metal soap powders) usable in the present cosmetic materials include powders of zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magensium myristate, zinc cetylphosphate, calcium cetylphosphate and zinc sodium cetylphosphate.
Examples of colored pigments usable in the present cosmetic materials include inorganic red pigments, such as iron oxide, iron hydroxide and iron titanate; inorganic brown pigments, such as xcex3-iron oxide; inorganic yellow pigments, such as iron oxide yellow and loess; inorganic black pigments, such as iron oxide black and carbon black; inorganic violet pigments, such as manganese violet and cobalt violet; inorganic green pigments, such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate; inorganic blue pigments, such as Prussian blue and ultramarine blue; lakes of tar pigments; lakes of natural dyes; and synthetic resin powders combined with the inorganic pigments as recited above.
Examples of pearl pigments usable in the present cosmetic materials include titanium oxide-coated mica, bismuth oxychloride, titanium oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish scales, and titanium oxide-coated colored mica; and examples of metallic powder pigments usable herein include aluminum powder, copper powder and stainless powder.
Examples of tar pigments which can be used in the present cosmetic materials include Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206 and Orange No. 207; and examples of natural pigments usable herein include powders of carminic acid, laccaic acid, carthamin, bradilin and crocin.
Additionally, the powders as recited above can be formed into complexes unless the resultant complexes weaken the effects of the invention, or those obtained by treating the powders as recited above with general oil, silicone oil, a fluorine-containing compound or a surfactant can also be used. Further, the powders as recited above can be used alone, or as a mixture of two or more thereof, if desired.
Examples of alcohols which can be used include lower alcohols, such as ethanol and isopropanol; sugar alcohols, such as sorbitol and maltose; and sterols, such as cholesterol, sitosterol, phytosterol and lanosterol.
Examples of water-soluble polymers which can be used include vegetable polymers, such as gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed, starch (rice, corn, potato, wheat), alge colloid, tranto gum and locust bean gum; microbial polymers, such as xanthan gum, dextran, succinoglucan and pullulan; animal polymers, such as collagen, casein, albumin and gelatin; starch polymers, such as carboxymethyl starch and methylhydroxypropyl starch; cellulose polymers, such as methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, crystalline cellulose and powdery cellulose; alginic acid polymers, such as sodium alginate and propylene glycol ester of alginic acid; vinyl polymers, such as polyvinyl methyl ether and carboxyvinyl polymer; polyoxyethylene polymers; polyoxyethylene-polyoxypropylene copolymers; acrylic polymers, such as sodium polyacrylate, polyethyl acrylate and polyacrylamide; polyethyleneimines; cationic polymers; and inorganic water-soluble polymers, such as bentonite, aluminum magnesium silicate, montmorillonite, beidellite, nontronite, saponite, hectorite and silicic acid anhydride.
In these water-soluble polymers, film-forming agents, such as polyvinyl alcohol and polyvinyl pyrrolidine, are also included.
The unctuous agents in any of solid, semisolid and liquid states can be used in the present cosmetic materials so far as they have so far been used for general cosmetics. More specifically, not only natural animal and vegetable fats and oils but also semi-synthetic fats and oils can be mixed in the present cosmetic materials. Examples of unctuous agents usable herein include avocado oil, linseed oil, almond oil, Chinese wax, perilla oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candellila wax, beef tallow, beef foot fat, beef bone fat, hydrogenated beef tallow, apricot kernel oil, spermaceti, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugar cane wax, sasanqua oil, safflower oil, shea butter, Chinese tung oil, cinnamon oil, jojoba wax, squalene, shellac wax, turtle oil, soybean oil, tea seed oil, tsubaki oil, evening primrose oil, corn oil, lard, rape seed oil, Japanese tung oil, rice-bran wax, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hydrogenated castor oil, methyl ester of caster oil fatty acid, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia nut oil, beeds wax, mink oil, cottonseed oil, cotton wax, Japan wax, haze kernel oil, montan wax, coconut oil, hydrogenated coconut oil, tricoconut oil fatty acid glyceride, mutton-tallow, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, polyethylene glycol lanolin fatty acid, POE hydrogenated lanolin alcohol ether, and egg yolk oil. Additionally, the term POE used herein stands for polyoxyethylene.
Examples of hydrocarbon oil which can be used herein include ozokerite, squalane, squalene, ceresine, paraffin, paraffin wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax and Vaseline; and examples of higher fatty acid which can be used include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid and 12-hydroxystearic acid.
Examples of higher alcohol which can be used herein include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol) and monooleyl glyceryl ether (cerakyl alcohol).
Examples of ester oil which can be used herein include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, N-alkylglycol monoisostearates, isocetyl isostearate, trimethylolpropane triisostearic acid ester, ethylene glycol di-2-ethylhexanoic acid ester, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoic acid ester, pentaerythritol tetra-2-ethylhexanoic acid ester, cetyl octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, neopentyl glycol dicapric acid ester, triethyl citrate, 2-ethylhexyl cinnamate, amyl acetate, ethyl acetate, butyl acetate, isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearate, dipentaerythritol fatty acid esters, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethylocanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutaminic acid 2-octyldodecyl ester and diisostearyl malic acid; and examples of glyceride oil which can be used herein include acetoglyceride, triisooctanoic acid glycride, triisostearic acid glyceride, triisopalmitic acid glyceride, monostearic acid glyceride, di-2-heptylundecanoic acid glyceride, trimyristic acid glyceride and myristic acid isostearic acid diglyceride.
Examples of silicone oils which can be used herein include organopolysiloxanes having from low to high viscosities, such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane and copolymer of dimethylsiloxane and methylphenylsiloxane; cyclic siloxanes, such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and tetramethyltetrahydrogencyclotetrasiloxane; silicone rubber, such as gummy dimethylpolysiloxane having a high polymerization degree and gummy copolymer of dimethylsiloxane and methylphenylsiloxane; cyclosiloxane solutions of silicone rubber; trimethylsiloxysilicate; cyclosiloxane solutions of trimethylsiloxysilicate; higher alkoxy-modified silicones, such as stearoxysilicone; higher fatty acid-modified silicones; alkyl-modified silicones; amino-modified silicones; fluorine-modified silicones; and silicone resin solutions. And examples of a fluorine-containing unctuous agaent which can be used herein include perfluoropolyether, perfluorodecaline and perfluorooctane.
Examples of an oil-soluble gelling agent which can be used herein include metal soaps, such as aluminum stearate, magnesium stearate and zinc myristate; amino acid derivatives, such as N-lauroyl-L-glutamic acid and xcex1,xcex3-di-n-butylamine; dextrin fatty acid esters, such as dextrin palmitic acid ester, dextrin stearic acid ester and dextrin 2-ethylhexaminic acid palmitic acid ester; sucrose fatty acid esters, such as sucrose palmitic acid ester and sucrose stearic acid ester; benzylidene derivatives of sorbitol, such as monobenzylidene sorbitol and dibenzylidene sorbitol; and clay minerals modified with organic compounds, such as dimethylbenzyldodecyl ammonium montmorillonite clay and dimethyldioctadecyl ammonium montmorillonite clay. These gelling agents can be used alone or as a mixture of two or more thereof, if desired.
In addition to the ingredients recited above, the present cosmetic materials can contain surfactants. The surfactants used in the invention have no particular restriction, but they may be any of anionic, cationic, nonionic and amphoteric ones so long as they have hitherto been used in general cosmetics.
Examples of anionic surfactants usable herein include fatty acid soap, such as sodium stearate and triethanolamine palmitate; carboxylates, such as alkyl ether carboxylic acids and salts thereof, and amino acid-fatty acid condensates; sulfonates, such as alkane sulfonates, alkene sulfonates, sulfonated fatty acid esters, sulfonated fatty acid amides, and alkylsulfonate-formaldehyde condensate; sulfates, such as alkylsulfates, higher secondary alcohol sulfates, alkyl and aryl ether sulfates, fatty acid ether sulfates, fatty acid alkylolamide sulfates, ether sulfates, and Turkeky red oil; phosphates, such as alkyl phosphates, ether phosphates, alkyl aryl ether phosphates, and amide phosphates; and active agents of N-acylamino acid type.
Examples of cationic surfactants usable herein include amine salts, such as alkylamie salts, polyamines and aminoalcohol fatty acid derivatives; quaternary alkylammonium salts; quaternary arylammonium salts; pyridinium salts; and imidazolium salts.
Examples of nonionic surfactants usable herein include sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, polyoxyalkylene-modified organopolysiloxanes, organopolysiloxanes modified with both polyoxyalkylene and alkyl groups, alkanolamides, sugar ethers and sugar amides; and examples of amphoteric surfactants usable herein include betaines, aminocarboxylate and imdazoline derivatives.
Examples of an ultraviolet absorbent which can be added include ultraviolet absorbents of benzoic acid type such as p-aminobenzoic acid, those of anthranilic acid type such as methyl anthranilate, those of salicylic acid type such as methyl salicylate, those of succinic acid type such as octyl p-methoxysuccinate, those of benzophenone type such as 2,4-dihydroxybenzophenone, those of urocanic acid type such as ethyl urocanate, and those of dibenzoylmethane type such as 4-t-butyl-4xe2x80x2-methoxydibenzoylmethane.
Examples of a moisture-holding agent which can be added include glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfuric acid, pyrrolidone carboxylate, polyoxyethylene methylglycoside, and polyoxypropylene methylglycoside.
Examples of an antiseptic agent which can be added include alkyl p-hydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate and phenoxyethanol; and examples of an antimicrobial agent which can be added include benzoic acid, salicylic acid, carbolic acid, sorbic acid, alkyl p-hydroxybenzoates, p-chlorometacresol, hexachlorophene, benzalkonium chloride, chlorohexidine chloride, trichlorocarbanilide, photosensitizer and phenoxyethanol.
Examples of an antioxidant which can be added include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene and phytic acid; examples of a pH regulator which can be added include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate and ammonium hydrogen carbonate; examples of a chelating agent which can be added include alanine, sodium ethylenediaminetetraacetate, sodium polyphosphate, sodium metaphosphate and phosphoric acid; examples of a refrigerant which can be added include L-menthol and camphor; and examples of an anti-inflammatory agent which can added include allantoin, glycyrrhizin, glycyrrhetinic acid, tranexamic acid and azulene.
Examples of skin-beautifying ingredients which can be added include whitening agents, such as placenta extract, arbutin, glutathione and Yukinoshita extract; cell activators, such as royal jelly, photosensitizer, cholesterol derivatives and calf blood extract; rough dry skin improvers; blood circulation improvers, such as nonylic acid vanillyl amide, benzyl nicotinate, xcex2-butoxyethyl nicotinate, capsaicin, zingerone, cantharis tincture, ichtammol, caffeine, tannic acid, xcex1-borneol, tocopheryl nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, tolazoline, acetyl choline, verapamil, cepharanthin and xcex3-oryzanol; skin astringents, such as zinc oxide and tannic acid; and anti-seborrheic agents, such as sulfur and thianthol.
Examples of vitamins which can be added include vitamin A, such as vitamin A oil, retinol, retinyl acetate and retinyl palmitate; vitamin B, including vitamin B2 such as riboflavin, riboflavin butyrate and flavin adenine nucleotide, vitamin B6 such as pyridoxine hydrochloride, pyridoxine dioctanoate and pyridoxine tripalmitate, vitamin B12 and its derivatives, and vitamin B15 and its derivatives; vitamin C, such as L-ascorbic acid, L-ascorbic acid dipalmitic ester, sodium (L-ascorbic acid)-2-sulfate and dipotassium L-ascorbic acid diphosphate; vitamin D, such as ergocalciferol and cholecarciferol; vitamin E, such as xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, dl-xcex1-tocopheryl acetate, dl-xcex1-tocopheryl nicotinate and dl-xcex1-tocopheryl succinate; vitamin H; vitamin P; nicotinic acids, such as nicotinic acid, benzyl nicotinate and nicotinic acid amide; pantothenic acids, such as calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether and acetylpantothenyl ethyl ether; and biotin.
Examples of an amino acid which can be added include glycine, valine, leucine, isoleucine, serine, threonine, phenylaranine, alginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, and tryptophan; examples of a nucleic acid which can be added include deoxyribonucleic acid; and examples of hormone which can be added include estradiol and ethenyl estradiol.
The term xe2x80x9ccosmetic materialxe2x80x9d as used herein are intended to include skin care products, such as face lotion, milky lotion, cream, face cleansing cream, massage materials, toilet soap and detergent, antiperspirant and deodorant; makeup products, such as face powder, foundation, rouge, eye shadow, mascara, eyeliner and lipstick; and hairdressing products, such as shampoo, rinse and treatment. Additionally, the present cosmetic material may have any of liquid, emulsion, solid, paste, gel and spray forms, if desired.
The present invention will now be illustrated in greater detail by reference to the following examples and comparative examples. However, the invention should not be construed as being limited to these examples.
Additionally, the entire disclosure of all applications, patents and publications, cited above and below, and of corresponding Japanese application No. 11-216619, filed on Jul. 30, 1999, is hereby incorporated by reference.